Composition of matter



Patented Dec. 24, 1940 COMPOSITION OF MATTER Melvin De Groote,University City, and Bernhard Keiser and Charles M. Blair, Jr., WebsterGroves, Mo., assignors to Pet'rolite Corporation, Ltd., Wilmington,Del., a corporation of Delaware No Drawing. Original application April19, 1939, Serial No. 268,818. Divided and this application January 26,1940, Serial No. 315,764

9 Claims.

This application is a division of our pending v application for patentSerial No. 268,818, filed April 19, 1939, for Process for resolvingpetroleum emulsions, which subsequently matured as U. S.

5v Patent No. 2,192,995, dated March 12, 1940.

The object of our present invention is to provide a new material orcomposition of matter,

that is particularly adapted for use as a demulsifler in the resolutionof crude oil emulsions, but

' 10 which may have uses in other arts that we have not yetinvestigated.

. The new composition of matter which constitutes our present inventionconsists of a certain kind of complex amine derived (a) by reactionbetween a polybasic carboxy acid body, such as phthalic anhydride, and(b) simpler amines of the kind hereinafter described. Said new compoundor composition of matter is particularly adapted for use as ademulsifier for crude oil ventional demulsifying agents of a compatibletype.

Attention is directed to our U. S. Patent No. 2,154,422, dated April 18,1939. In said patent ,2 there is described an amine summarized by thefollowing formula:

onncooomom m. in which m represents the numeral 1, 2 or 3, m representsthe numeral 0, 1 or 2, and m" represents the numeral 0, 1 or 2, with theproviso that m+m'+m=3. However, the radical C2H4, which appears in theabove formula, may represent any similar radical, such as a CaHeradical, C4Ha radical, etc., and therefore, the above formula may berewritten:

.55 as acetic acid, butyric acid, oleic acid, stearic emulsions, eitheralone, or in admixture with conacid, naphthenic acid, abietic acid, orthe like,

all of which are characterized by having less than 32 atoms. The alkylolradical, priorto acylation, may be a hydroxy alicyclic or a hydroxyaralkyl radical, provided that the hydroxy radical is attached to thealiphatic residue of the aralkyl radical. In the above formulas,OH.RCOOH represents a hydroxylated fatty acid, such as ricinoleic acid,hydroxystearic acid, dihydroxystearic acid, diricinoleic acid,triricinoleic acid, polyricinoleic acid, etc.; and OHRCOO represents theoxy acyl radical derived from such acid, 1. e., the ordinary acidradical. Blown oils (oxidized oils) are not included.

Similarly, attention is directedto our U. S. Patout No. 2,154,423, datedApril 18, 1939. In said last mentioned patent there are describedcompounds which may be summarized by the following formula:

(R.coo.c,m)..

(OH.C:HA)-' in which m represents the number 1 or 2, m.

represents the number 1 or 2, and m" represents the number 0 or 1, withthe proviso that m+m'+m"=3.

However, the radical C2H4, which appears in the above formula, mayrepresent any similar radical, such as a CaHc radical, a CsHs radical,etc., and therefore, the above formula may be rewritten:

where n represents a small whole number, preferably not over 10. a

In the above group, T represents a hydrogen atom or an aliphatichydrocarbon radical, such as a methyl, ethyl, propyl, amyl, or similarradical; or '1 may represent a non-hydroxy alicyclic radical, such as acyclohexyl radical, or a nonhydroxy aralkyl radical, such as a benzylradical; or the acylated radical obtained by replacing a hydrogen atomof the hydroxyl group of an alkylol radical by the acyl radical of amonobasic cal-boxy acid, such as acetic acid, butyricacid, heptoic acid,or the like, all of which are characterized by having less than 8 carbonatoms. The alkylol radical, prior to acylation, may be a hydroxyalicyclic or a hydroxy aralkyl radical, provided that the hydroxyradical is attached to the aliphatic residue of the aralkyl radical.

In the above formula, R.COO represents the oxy-acyl or acid radicalderived from the acid R.COOH. R.COOH represents any monobasicdetergent-forming carboxy acid, such as a typical fatty acid or abietic'acid or naphthenic acid. Typical fatty acids are those which occur innaturally-occurring oils and fats, and generally have .8 or more carbonatoms, and not over 32 carbon atoms. Common examples include oleic acid,stearic acid, linoleic acid, linolenic acid, ricinoleic acid, erucicacid, palmitic acid, myristic acid, etc. These acids combine with alkalito produce soap or soap-like materials, and are commonly referred to asbeing monobasic detergent-forming carboxy acids. Blown oils (oxidizedoils) are not included.

In each of said U. S. Patents Nos. 2,154,422 and 2,154,423, both datedApril 18, 1939, attention is directed to the fact that having preparedthe relatively simple intermediate amine of the kind previouslydescribed, the second step in the preparation of the new compositions ofmatter is to produce an esterifled amine of the kind obtainable byreaction with a carboxy acid or its functional equivalent, such as ananhydride, with the proviso that such functional equivalent shall notinclude (a) the acid esters derived by reaction between a polybasicacid, such as phthalic acid or its anhydride, and an alcohol acid(hydroxy acid) such as ricinoleic acid and the like; or (b) the acidester derived by a reaction between a polybasic carboxy acid, such asphthalic acid and its anhydride, and a fractional ester of thedetergent-forming acid, such as mono-olein, mononaphthenin,mono-abi'etin, etc.

As to further details regarding the various monocarboxy acidic compoundswhich may be employed, as to the various amines which may be employed,and as to the various polybasic carboxy acids or their equivalents whichmay be employed, as well as the method of manufacture, reference is madeto the aforementioned patents, in which there are detailed descriptions.

For purposes of comparison, the two formulas which indicate thecomposition of the amines previously referred to are here repeated:

' volves a hydroxyl radical attached either to a hydroxy hydrocarbonradical, which replaces an amino hydrogen atom, or a hydroxyl radical,which is part of a hydroxy fatty acid, such as ricinoleic acid.

Reference is made to the fact that in both of said patents it is pointedout that some other residue may replace the residue indicated by theradical CnHml, and one example of such radical which may act as asubstitute for the Cal-ha radical is the radical OH.C3H5, which isderived from glycerylamine or diglycerylamine, or the like, instead ofbeing derived from ethanolamine, diethanolamine, or the like; all ofwhich is stated in said patents in the following language:

Attention is directed to the fact that the alkylolamines are obtained insuch a manner that they may be looked upon as being derivatives of wouldhave dihydric alcohols. or of the chlorhydrins of the dihydric alcohols.For example, the alkylolamines may be formed in the following manner:

' (omclnlffniriiuni As previously stated, the C2H4 radical may be anyone of a number of hydrocarbon radicals which are aliphatic, allcyclic,or aralkyl in nature.

"It is at once manifest that similar derivatives are available fromglycerols, polyglycerols, and the like, as indicated by the followingreaction:

omicmlici iriium "It is not necessary to point out that the same typesof reactions will produce secondary or tertiary amines, and that thereaction is not limited to a combination with ammonia, but may takeplace with a combination of other primary or secondary amines, such asamylamine, diamylamine, cyclohexylamine, dicyclohexylamine, benzylamine,dibenzylamine, amyl cyclohexylamine, etc.

This means that in the type of material previously described there is awide variety of material, such as monoglycerylamine, diglycerylamine,monoglyceryl diethylamine, monoglyceryl dipropylamine, diglycerylpropylamine, triglycerylamine, etc., which arefunctional equivalents ofthe various amines previously described for reaction with triricinoleinand the like. When such amines are employed, instead of the radicalCnH2n appearing in a compound, one in place thereof the radical-OH.CaHs-; or, in case the hydroxyl radicals of these OH.CaHsradical hadbeen removed by esterlfication with any available carboxyl, then thesubstituent which replaces the CnHZn radical might be indicated by theformula D.CaH5--. All that has been said here in regard to functionalequivalents will be perfectly obvious, without further explanation tothose skilled in the art. See U. S. Patent No. 2,091,704, dated August31, 1937, to Duncan and McAllister; and also U. S. Patent No. 2,042,621,dated June 2, 1936,

. i0 Olin.

An examination of the two summarizing formulas above indicated suggeststhat as far as derivatives of glycerylamine or their'functionalequivalents are concerned, one may obtain. products derived by reactionwith phthalic anhydride or the like, which are different from thecompositions of matter described in the co-pending applications in thefollowing respects: (a) they do not involve reaction with a hydroxyhydrocarbon radical which replaces an amino hydrogen atom, as, forinstance, an ethanol radical, and (b) they do not involve reaction withthe alcoholiform hydroxyl of a fatty acid radical, as, for instance, thehydroxyl of a ricinoleic acid radical. All of which is apparent uponexamination of the following formulas which indicate the nature of suchmaterials. It is understood that materials of the type of formulasubsequently included are analogs of materials of the type disclosed anddescribed in said co-pending applications, and may be prepared by thesame analogous methods. As to the general procedures employed forproducing the intermediate or complex amines which are subsequentlysubjected to esterlflcation with the polybasic carboxy acid, such asphthalic anhydride, reference is made to the aforementioned co-pendingapplications.

- Following the procedures of said co-pending applications, but usingglycerylamines or their functional equivalents instead, one may obtainedreagents exemplified by the following formulas erucic acid, palmiticacid, myristic acid, etc,

These acids combine with alkali to produce soap or soap-like materials,and are commonly referred to as being monobasic detergent-formingcarboxy acids. Blown oils (oxidized oils) are not included. Anexamination of the above formula indicates, however, that where an aminohydrogen atom exists, it may be replaced'by some other radical, providedthat the compound is still basic in character; for instance, thehydrogen atom may be replaced by an alkyl' radical, an

alicyclic radical, an aralkyl radical, or an acylated alkanol, providedthere is no free hydroxyl still attached to the alkanolamine radical,and provided that the acyl group is derived from any suitablenon-hydroxy acid such as acetic acid,

butyric acid, heptoic acid, or any of the detergent-forming monocarboxyacids previously described. All of which may be summarized by rewritingthe previous formulas in the following form:

I in which R'.COO is the acid radical derived from an acid having lessthan 8 carbon atoms. Other to any particular isomeric form, but oneisomer will serve as suitably as another.

[( 910 1Hs-0-CaHaOHIaN If, instead of a derivative of diglycerol, onecontemplates the equivalent amine derived from triglycerol, it isobvious that the counterpart'of the'last preceding formula is asfollows:

It is to be noted that the difference between the amines derived frompolyglycerolamines, as distinguished from those derived-from glycerol,

is that the hydrocarbon radical is interrupted at I least once by anoxygen atom. Forthe sake of simplicity, the residue to which the aminonitrogen atom is attached and to which the hydroxyl radicals are alsoattached, will be referred to as a hydrocarbon radical, but it isunderstood that the word "hydrocarbon," as herein employed, includingthe appended claims, is intended to include the hydrocarbon radicalswhich are interrupted at least once by an oxygen atom.

For the sake of convenience, the previous formulas, that is, theformulas of the various glycerylamines, or their functional equivalents,may be indicated as follows:

in which D is a hydrocarbon residue, n refers to the numeral 1 to 4, mrepresents the numeral 1 to 3, and 111. represents the numeral to 2.When such amines are treated with a detergentforming acid, or stillbetter, the ester of a detergent- -forming acid, in the manner describedin our previously mentioned patents, one obtains compounds in which oneor more of the hydroxyl radicals attached to'the radical D are replacedby non-hydroxylated detergent-forming mono carboxy acid radicalsindicated by the formula R'.C0O,- and one or more of the remaininghydroxyls may be replaced by radicals such as R".COO derived from aceticacid or some similar acid having less than 8 carbon atoms. Note thepresent significance of R and R. All of this may be indicated in oneformrby the following formula:

in which n represents the numeral 1 to 4, n" the numeral 0 to 3, n'" thenumeral 0 to 3, m the numeral 1 to 3, and m the numeral 0 to 2, with theproviso that at least one occurrence of D must have at least onehydroxyl radical attached thereto. As has been previously pointed out,instead of the amino hydrogen atom, one may have in place thereof anysuitable radical, such as an alkyl radical, aralkyl radical, or any oneof number of other radicals, except an aryl radical, because the arylradical destroys or substantially eliminates the basicity of thenitrogen atom. What has been said previously may be indicated by againrewriting the formula immediately preceding, as follows:

If one rewrites the formula for the glycerylamine or its homolog or thelike in the following manner:

in which n represents the numeral 1 to 4, m the numeral 1 to 3, and mthe numeral 0 to 2, and if for the moment one limits consideration toglycerylamines or the likewhich happen to be tertiary amines, thatis, tosuch instances in. which there is no amino hydrogen atom present, thencompounds of the kind herein contemplated can be made from such amineswith the same case as they can be derived from the comparable tertiaryamine, triethanolamine or monoforming acids or compounds and thetertiary" described in said co-pending applications previouslymentioned.

Attention is directed to the following analogous reactions which appearin our prior patents previously mentioned, and which can be adapted justas suitably to the pre'esnt instance by replacing triethanolamine or thelike with a glycerylamine, provided that'it is a tertiary amine, such asdiamylglycerylamine, amyl diglycerylamine, triglycerylamine, or thelike, and provided at least one radical replacing an amino hydrogenradical represents a polyhydroxylated hydrocarbon radical, and providedthat after reaction with the selected acid compounds, such as an ester,that there is attached at least one hydroxyl radical to the acylatedhydrocarbon radical, which, in turn, is attached to the amino nitrogenatom. In other words, when reactions of the kind described in our priorpatents previously mentioned are adapted to the present instance, thereactions between the suitable detergentglyceryl amines or the likeresult in compounds which may be indicated in their simplestiorm by thefollowing formulas (as previously noted),

' and which will again be repeated.

If, however, one does not employ tertiary amines, but does employprimary or secondary amines, then in that event, other procedure may beemployed to produce the desired type of compound in significant yield.Reference is made to the following equations:

OH OH ]+NH: -r R.CO0.CIHi Cl H R.COO.CaHi

.allcyl diethanolamine or dialkylethanolaminejas If, however, maximumyields are not necessary, one need not resort to reactions of the kindpreviously described to produce primary or secondary amines, but one mayemploy the following type oi It is also to be noted that various otherfunc tional equivalents may be employed, for instance, there areavailable substituted or alkyl glycerols, such.as propylglycerol,butylglycerol, and octylglycerol, or the like, in which such hydrocarbonradicals or other similar hydrocarbon radicals replace a hydrogen atomof the glyceryl radical. It is also known that glyceryl amines may betreated with alkylene oxides, such as ethylene oxide, to producederivatives or substituted mono or diglycerylamines, in which one orboth amino hydrogen atoms have been replaced by an bydroxy alkylradical, and presumably similar derivatives are available in which theremight be 'present an hydroxy alicyclic or hydroxyl aralkyl radical,instead of an hydroxyl alkyl radical. In the hereto appended claims, theword alkanol is intended to include hydroxy alicyclic and hydroxyaralkyl compounds. Various other variants suggest themselves, in view ofwhat has been said here, and in view of the analogous reactions orcompounds suggested in the previously mentioned co-pending applications.It is to be noted that all the amines of the kind described are basic incharacter, and that they do not contain the amide radical. It is to benoted that they are not quaternary ammonium bases, and that they arederived only from basic amines; it is to be further noted that theesterified amine has not lost any of the basicity of the original amine,and that said amines exhibit the property of a basic amine, that is,they combine with water to form a base which is presumably a substitutedammonium compound. For further elaboration in regard to what has justbeen said, reference is again made to the analogous compounds describedin our U. S. patents aforementioned.

Our preference is to manufacture the compounds in question by producingan intermediate amine by reaction between an ester and a tertiary amine,although it is understood that any of the procedures previouslydescribed may be employed. If derived from the fatty acids, thenaturallyoccurring glycerides are employed. It derived from petroleumacids, such as naphthenic acids, or from rosin acids, such as abieticacid, then any suitable ester, such as an ester derived from glycerol,ethylene glycol, or a monohydric alcohol, such as ethyl alcohol, may beemployed.

The manufacture of intermediate compounds from tertiary amines isrelative simple, because no precautions are necessary to preventamidification. The selected non-hydroxy fatty oil, if such be employed,and the selected tertiary amine, are mixed together in suitableproportions and heated at some point above the boiling point of water,for instance, C., and at a point below the decomposition point of theamine or the fatty oil, for instance, C., for a suitable period of time,such as two to eight hours. Mild agitation is employed. A catalyst, suchas sodium oleate, sodium carbonate, caustic soda, etc., may be presentin amounts of about one-half ofone percent or less. It is to be notedthat the fatty acids are employed in this instance in the form of anester, to wit, the glyceride, although, as previously pointed out, otherfunctional equivalents can be readily employed with equal facility,provided that the acyl radical R.CO. is present. It is to be noted thatthe reactions above described do not take place to any appreciableextent, if the taken so that one obtains a substantial percentage ofproducts derived by esterification, rather than amidification. Anysuitable ester may be employed, but'it is most convenient to use theester of a fatty acid, for instance, olein.

In order to illustrate suitable examples of the amines which may be usedas intermediate raw materials, the following examples are given:

Intermediate amine-Example 1 Olein is employed. For convenience, itsmolecular weight is considered as 8'75. Amyl diglycerylamine and oleinin the proportion ofone mol of olein to one mol of amyldiglycerylamineare heated at a temperature between 150 degrees and 180 degrees C. forabout 2 hours. Mild agitation is employed. The mono-hydroxy reactionproduct so produced may be used as such in subsequent reactions, or maybe converted into the acetate, or some other suitable form. The productis characterized by freedom from non-' acylated hydroxyl hydrocarbonradicals. The composition of this type of material may be ex emplifledby the following structural formula:

pound.

Intermediate amine-Example 3 Ethyl stearate is employed in the properstoichiometrical ratio, instead of olein, as in Examples 1 and 2 above.

Intermediate amine-Example 4 Ethylene glycol dipalmitate is employed insuitable proportions in Examples 1 and 2, previously described.

Intermediate amine-Example 5 Methyl naphthenate in proper proportions isused to replace olein in Examples 1 and 2.

Intermediate amine-Example 6 functional equivalent shall not include (a)the acid esters derived by reaction between a polybasic acid, such asphthalic acid or its anhydride,

derived by a reaction between a polybasic carboxy acid, such as phthalicacid and its anhydride, and a fractional ester of the detergentforming'acid, such as mono-olein, mono-naphthenin, mono-abietin, etc.

The polybasic carboxy acids which may be employed, including some havingat least three carboxyl radicals, are phthalic, succinic, malic,fumaric, citric, maleic, adipic, tartaric, glutaric, diphenic,naphthalic, oxalic. etc.

Having prepared the intermediate amines above described, it is onlynecessary to react such amines with the selected polybasic carboxy acidor its functional equivalent in such a manner as to produce anesterifled product 'as differentiated from a salt. There is no objectionto salt formation, provided that esteriflcation also takes place.

Composition of matter-Example 1 changed so that the amount of phthalicanhydride is decreased slightly. A- suitable solvent may be present, andany water formed may be distilled oil continuously during theesterification process. The solvent may remain behind in the finalproduct, or may be removed, if desired.

If desired, the acidic mass may be neutralized" with any suitable amine,such as triethanolamine, cyclohexylamine, triamylamine, etc.

Composition of matter-Example 2 Butyl acid phthalate is substituted forphthalic anhydride in the previous exam ple.

Composition of matter-Example 3 Potassium acid phthalate is substitutedfor phthalic anhydride in Composition of matter- Example 1 above.

Composition of matterEa:ample 4 The same procedure is followed as inComposition of matter-Example 1 above, except that no solvent isemployed, and when the reaction is complete, one mol or slightly less ofglycerol is added and esterification continued until all the glycerolpresent is chemically combined.

Composition of matter-Brample 5 Ethylene glycol is substituted forglycerol in Composition of matter-Example 4 immediately preceding.

Composition of matter-Example 6 Diethylene glycol is substituted forglycerol in Composition of matter-Example 4 immediately preceding. r

Composition of matterExample 7 The monoethyl ether derivative ofethylene glycol is employed in place of glycerol in Composition ofmatter-Example 4 above.

Composition of matter- -Emample 8 Composition of matter-Example 9 Oleylalcohol is substituted for glycerol in Composition of matter-Example 4above.

Composition of matter-Example 10 Composition of matter-Example 11 Citricacid is substituted for phthalic acid in Composition of matterExamples1-9, inclusive.

Composition of matter-Example 12 Other intermediate amines of the kinddescribed under the headings Intermediate amine-Examples 2-6, inclusive,are substituted for intermediate amines in the prior examples.

It is evident that where reference is made to phthalic acid, some simplederivative, such as chlorinated phthalic acid, brominated phthalic acid,methylated phthalic acid, or the like, would simply act as a functionalequivalent. This applies not only to phthalic acid, but all thepolybasic acids enumerated or suggested. Similarly, it is evident thatthere is no intention to differentiate between isomeric forms. Oneisomeric form may serve as well as another.

We desire to emphasize that the products obtained in the above examples,when employed as demulsiflers to resolve a petroleum emulsion, may beused in the form of the amine by direct contact with the emulsionwithout contact with water. It may be contacted with water, i. e., inthe form of a solution so as to produce, in a greater or lesser degree,the amine base. Furthermore,-

any of the products above described may be combined with a suitableacid. Acetic acid may be employed. Hydrochloric acid is particularlydesirable. In some instances acids, such as oleic acid or naphthenicacid, may be employed to give a suitable salt. As previously pointedout, any carboxylic hydrogen atom may be replaced by a suitable metallicatom, or an organic radical derived from an alcohol, or from an amine.All such ionizable hydrogen atom equivalents are considered as thefunctional equivalent of the ionizable hydrogen atoms themselves, andsuch neutralized forms are included in the scope of the appended claimsas the equivalent of the acidic form. The expression detergent-formingacid compound is employed to include the acid itself, as well assuitable compounds thereof. It is realized that where a free carboxyland a basic amine residue exists in the same molecule, there may be atendency towards the formation of inner salts comparable to sulfanilicacid; but due to the size of the molecule involved, and perhaps forreasons of steric hindrance, We' are not aware that such inner salts areformed.

Briefly, then, the preparation of the composition of matter hereincontemplated depends on a reaction involving a polybasic carboxy acidbody, or its functional equivalent, as described, and the complex amineof the kind described, in such a manner as to involve reactions otherthan salt formation. In other words, the complex amines are basic innature, and therefore, could react with a polybasic acid to form a saltin is manner, which, for the sake of convenience, will thus:

COOH

COOH

Such reactions are purely salt formation. The materials of the kindherein contemplated, regardless of their nature, are of the kindobtained by reactions other than salt formation, and also other thanamidiflcation.

We desire to emphasize that the expression "polybasic carboxy acid,"employed in the claims, refers not only to the acid itself, but to anyfunctional equivalent, such as the anhydride, the acyl chloride, a saltform having at least two free carboxyls, such as mono-sodium citrate,etc. It is also understood that in the hereto appended claimsthe natureof the final product is not limited to the form having a free carboxylichydrogen atom, but that such free carboxylic hydrogen atom may beactually replaced by any functional equivalent of the kind previouslydescribed, for instance, a metallic atom, an ammonium radical, an amineradical, such as an amylamine radical. benzylamine radical, ethanolamineradical, diethanolamine radical, triethanolamine radical, a hydrocarbonradical, such as an ethyl, methyl, propyl, or amyl radical, a radicalderived from ethylene glycol, glycerol, or the like; a cyclohexylradical, benzyl radical, etc. All such forms in which such hydrogen atomequivalent replaces an ionizable hydrogen atom, are obvious functionalequivalents.

Attention is directed to the fact that the word amidiflcation has beenapplied to the reaction involving the replacement of an amine hydrogenatom by an acyl radical,without conventional limitation to a reactioninvolving. ammonia. The replacement of the amino hydrogen atom of aprimary amine or a secondary amine by an acyl radical has beenconsidered as being amidification, rather than the formation of asubstituted amide, or the formation of an imide or substituted imide.Such obvious departure from conventional nomenclature has been forpurposes of simplicity and to show the similarity between certainreactions.

In the hereto appended claims, reference'to the product derived byreaction between a polybasic carboxy acid body of the kind previouslydescribed and an amine'of the kind previously described is meant torefer to such products in all their various modifications previouslyreferred to, to wit, such substances where carboxylic hydrogen atomsappear as such, or have been replaced by metallic atoms, alkyl radicalsderived from various alcohols, amine radicals or residues, etc.; and asto the presence of any basic aminenitrogen atom, it may be in the amineform, or in salt form, or in a base form, as, for example, is obtainableby contact with water.

The functional equivalents of all these variations have been pointed outpreviously and are readily comprehended; and the scope of the claims inthe light of such obvious equivalents requires no further discussion.

As to blown oils, blown fatty acids, polymerized oils, polymerized fattyacids, and other similar materials obtainable by oxidation, it isunderstood thflt it is not intended that they should be reacted withamines to produce the intermediate amine, which, in turn, is reactedwith azpolybasic carboxy acid to produce the new composition of matter.

For convenienc in the hereto appended claims the expression hydrocarbonradical derived from a glycerylamine is intended to include the varioushomologs and analogs of glycerylamine, and thus, is used in the genericsense 10 to' include the glycerylamines derived from diglycerol,triglycerol, etc., as well as the more common glycerylamines derivedfrom glycerol. Where the hydrocarbon radical from conventionalglycerylamine is intended, reference will be made to the C3H5 radical.

Attention-is directed toth'e fact that in at least part of the heretoappended claims reference is made to an acyl radical R.CO derived from adetergent-forming acid, and similarly,

reference is made to the acid radical RCOO derived from an acid such asacetic acid, butyric acid, and the like, and it is to be noted wheresuch radicals occur more than once in the finished product or completedmolecule, that such repeated occurrences need not be identical, forinstance, in such cases where R.CO appears more than once, it may in oneinstance, be derived from oleic acid, in the second instance, frompalmitic acid, etc., and where R'COO occurs more than once, it may bederived'in one instance from acetic acid, in the second instance frombutyric acid, etc.

Conventional demulsifying agents employed in the treatment of oil fieldemulsions are used as such, or after dilution with any suitable solvent,

such as water, petroleum hydrocarbons, such as "gasoline, kerosene,stove oil, a coal tar product, such as benzene, toluene, xylene, taracid 011, cresol; anthracene oil, etc. Alcohols, particularly aliphaticalcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol,propyl alcohol,

butyl alcohol, hexyl alcohol, octyl alcohol, etc., may be employed asdiluents. Miscellaneous solvents, such as pine oil, carbontetrachloride, sulfur dioxide extract obtained in the refining ofpetroleum, etc., may be employed as diluents. Similarly, thematerial ormaterials herein described may be-admixed' with one or more of thesolvents customarily used in connection with conventional -demulsifyingagents. Moreover,

said material or materials may be used alone,

or in admixture with other suitable well known classes of demulsifyingagents.

It is well knownthat conventional demulsifying 5 agents may be used in awater-soluble form, or

. fact is true in regard to the material or materials herein described.

We desire "to point out that the superiority of the herein describedmaterial as a demulsifier for petroleum emulsions, is based uponitsability to treat certain emulsions more advantageously and at asomewhat lower cost than is possible with other available demulsifiers,or conventional mixtures thereof. It is believed that th e'particulardemulsifying agent or' treating agent "(I herein described will findcomparatively limited application, so far as the majority of oil fieldemulsions are concerned; but we have found that such a demulsifyingagent has commercial value, as it will economically break or resolve oilfield emulsions in a number of cases which cannot be 5 treated as easilyor at so low a cost with the demulsifying agents heretofore available.In using our new material or composition of matter to break a petroleumemulsion, said material is brought into-contact with or caused to 10 actupon the emulsion to be treated, in any of the various ways or by any ofthe various apparatus now generally used to resolve or break petroleumemulsions with a chemical reagent, the above procedure being used eitheralone, min 15 combination with other. demulsify'ing procedure, such asthe electrical dehydration process.

Having thus described our invention, what we claim as new anddesire tosecure. by Letters Patent is: 20

. 1. A product derived by an esteriflcation reaction between: first, apolybasic carboxy acid compound characterized by: (a) the presence of atleast one free carboxyl radical; (b) the absence of any hydroxy fattyacid radical as a substituent 25 for an acidic hydrogen atom of anycarboxyl radical; and (c) the absence of any polyhydric alcohol radicalas the substituent for an acidic hydrogen atom of any carboxyl radicalif said polyhydric alcohol radical is also united with 30 one or moremonobasic carboxy detergent-forming acid radicals; and second, anacylated hydroxy amine derived by esterification reaction between; (A) adetergent-forming acid compound contain- 5 ing the acyl radical R.CO, inwhich R is a hydro- 35 carbon radical containing at least 8 carbon atomsand not more than 32 carbon atoms; and (B) an amine of the formula type:

uaccooinmommn'urm' in which R is a hydrocarbon radical containing lessthan 8 carbon atoms, D is a hydrocarbon radical derived from aglycerylamine, T is a monovalent radical selected from the class con-psisting of alkyl radicals, alicyclic radicals, aralkyl radicals,non-hydroxylated acylated alkanol radicals and hydrogen atoms, and nrepresents the numeral 0 to 3, m represents the numeral 1 to 4. mrepresents the numeral 0 to 3, and n represents the numeral 1 to 3, withthe proviso that n+m'=3, and said acylated hydroxy amine beingadditionally characterized by absence of any, unacylated hydroxysubstituted hydrocarbon radicals.

2. A product derived by an esterification reaction between: first, apolybasic carboxy acid compound characterized by: (a) the presence of atleast one free carboxyl radical; (b) the absence of any hydroxy fattyacid radical as a substituent for an acidic hydrogen atom of anycarboxyl radical; and (.c) the absence of any polyhydric alcohol radicalas the substituent for an acidic hydrogen atom of any carboxyl radicalif said polyhydric alcohol radical is also united with one or moremonobasic carboxy detergent-forming acid radicals; and second, anacylated hydroxy amine derived by esterification reaction between: (A) adetergent-forming acid compound containing the acyl radical R.CO, inwhich R is a hydrocarbon radical containing at least 8 carbon atoms andnot more than 32 carbon atoms; and (B) an amine of the formula typez'[(R'.C0O)11D(OH) m]n'NTm' inwhich R. is a hydrocarbon radical containingless than 8 carbon atoms, D is a hydrocarbon radical derived from aglycerylamine, T is a monovalent radical selected from the classconsisting of alkyl radicals, alicyclic radicals, aralkyl radicals, andnon-hydroxylated acylated alkanol radicals, and n represents the numeral0 to 3, m

represents the numeral 1 to 4, m represents the numeral 0 to 2, and nrepresents the numeral 1 to 3, with the proviso that n'+m'=3, and saidacylated hydroxy amine being additionally characterized by absence ofany unacylated hydroxy substituted hydrocarbon radicals.

3. A product derived by an esterification reac-- tion between: first, apolybasic carboxy acid compound characterized by: (a) the presence of atleast one free carboxyl radical; (b) the absence of any hydroxy fattyacid radical as a substituent between: (A) a detergent-forming acidcompound containing the acyl radical RCO, in which R is a hydrocarbonradical containing at least 8 carbon atoms and not more than 32 carbonatoms; and (B) an amine of the formula type:

in which D is a hydrocarbon radical derived from a glycerylamine, T is amonovalent radical selected from the class consisting of alkyl radicals,

=alicyclic radicals, aralkyl radicals, and nonhydroxylated acylatedalkanol radicals, and m represents the numeral 1 to 4, m represents thenumeral 0 to 2, and n represents the numeral 1 to 3, with the provisothat n'+m'=3, and said acylated hydroxy amine being additionallycharacterized by absence of any unacylated hydroxy substitutedhydrocarbon radical.

4. A product derived by an esteriflcation reaction between: first, apolybasic carboxy acid compound characterized by: (a) the presence of atleast one free carboxyl radical; (b) the absence of any hydroxy fattyacid radical as a substituent for an acidic hydrogen atom of anycarboxyl radical; and (c) the absence of any polyhydric alcoholradical-if said polyhydric alcohol radical is also united with one ormore monobasic carboxy detergent-forming acid radicals; and second, anacylated hydroxy amine derived by esterification reaction between: (A) afatty acid compound containing the acyl radical R.CO, in which R is ahydrocarbon radical containing at least 8 carbon atoms and not more than32 carbon atoms; and (B) an amine of the formula type in which D is ahydrocarbon radical derived from a glycerylamine, T is a monovalentradical selected from the class consisting of alkyl radicals, alicyclicradicals, arallnyl radicals, and non-hydroxylated acylated alkanolradicals, and m represents the numeral 1 to 4, 111. represents thenumeral 0 to 2, and n represents the numeral 1 to 3, with the provisothat n'+m'=3, and said acylated hydroxy amine being additionallycharacterized by absence of any unacylated hydroxy substitutedhydrocarbon radical.

5. A product derived by an esterification reaction between: first, adibasic carboxy acid compound characterized by: (a) the presence of atleast one free carboxyl radical; (b) the absence of any hydroxy fattyacid radical as a substituent for an acidic hydrogen atom of anycarboxyl radical; and (c) the absence of any polyhydric alcohol radicalif said polyhydric alcohol radical is also united with one or moremonobasic carboxy detergent-forming acid radicals; and second, anacylated hydroxy amine derived by esterification reaction between? (A) afatty acid compound containing the acyl radical RCO, in which R is ahydrocarbon radical containing at least 8 carbon atoms and not more than32 carbon atoms; and (B) an amine of the formula type in which D is ahydrocarbon radical derived from a glycerylamine, T is a monovalentradical selected from the class consisting of alkyl radicals, alicyclicradicals, aralkyl radicals, and non-hydroxylated acylated alkanolradicals, and m represents the numeral 1 to 4, 112' represents thenumeral 0 to 2, and n represents the numeral 1 to 3, with the provisothat n'+m'=3, and said acylated hydroxy amine being additionallycharacterized by absence of any unacylated hydroxy substitutedhydrocarbon radical.

6. A product derived by an esteriflcation reaction between: first,phthalic anhydride; and second, an acylated hydroxy amine derived byesterification reaction between: (A) a fatty acid compound containingthe acyl radical R.C0, in which R is a hydrocarbon radical containing atleast 8 carbon atoms and not more than 32 carbon atoms; and (B) an amineof the formula type:

in which D is a hydrocarbon radical derived from a. glycerylamine, T isa monovalent radical selected from the class consisting of alkylradicals, alicyclic radicals, aralinvl radicals, and non-hydroxylatedacylated alkanol radicals, and 121. represents the numeral 1 to 4, 1nrepresents the numeral 0 to 2, and t represents the numeral l to 3, withthe proviso that n'+m'=3, and said acylated hydroxy amine beingadditionally characterized by the absence of any unacylated hydroxysubstituted hydrocarbon radical.

7. A product derived by an esterification reaction between: first,phthalic anhydride; and second, an acylated hydroxy amine derived byesterification reaction between: (A) a fatty acid compound containingthe acyl radical R.CO, in which R is a hydrocarbon radical containing atleast 8 carbon atoms and not more than 32 carbon atoms; and (B) an amineof the formula type:

[(OHhCaHsLuNTw in which T is a monovalent radical selected from theclass consisting of alkyl radicals, alicyclic radicals, aralkylradicals, and non-hydroxylated acylated alkanol radicals, and mrepresents the numeral 0 to 2, and n represents the numeral 1 to 3, withthe proviso that n+m'=3, and said acylated hydroxy amine beingadditionally characterized by absence of any dihydroxypropyl radical.

8. A product derived by esterification reaction between: first, phthalicanhydride; and second, an acylated hydroxy amine derived byesterification reaction between: (A) an oleic acid compound containingthe oleyl radical;

and (B) an amine of the formula type:

in which T is a monovalent radical selected from the class consisting ofalkyl radicals, alicyclic radicals, aralkyl radicals, and acylatedalkanol radicals, and m represents the numeral 0 to 2, and n representsthe numeral l-to 3, with the proviso that n'+m'=3, and said acylatedhydroxy amine being additionally characterized by absence of anydihydroxypropyl radical.

9. A product derived by an esterification reaction between: first,phthalic anhydride; and second, an acylated hydroxy amine derived bycompound containing the oleyl radical;

, .9 esteriflcation reaction between: (A) an oleic acid an amine of theformula type:

Homzcmam'rm' in which T is a monovalent alkyl radical, and m representsthe numeral 0 to 2, and n represents the numeral 1 to 3 with the provisothat n'+m'=3, and said acylated hydroxy amine and (3) being additionallycharacterized by absence of -m a dihydroxypropyl radical.

mm DE GROOTE. BERNHARD KEISER. CHARLES M. BLAmJR.

